Methods for improving the quality of structures comprising semiconductor materials

ABSTRACT

Methods which can be applied during the epitaxial growth of semiconductor structures and layers of III-nitride materials so that the qualities of successive layers are successively improved. An intermediate epitaxial layer is grown on an initial surface so that growth pits form at surface dislocations present in the initial surface. A following layer is then grown on the intermediate layer according to the known phenomena of epitaxial lateral overgrowth so it extends laterally and encloses at least the agglomerations of intersecting growth pits. Preferably, prior to growing the following layer, a discontinuous film of a dielectric material is deposited so that the dielectric material deposits discontinuously so as to reduce the number of dislocations in the laterally growing material. The methods of the invention can be performed multiple times to the same structure. Also, semiconductor structures fabricated by these methods.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/106,647 filed May 12, 2011, which is a continuation-in-part of U.S.application Ser. No. 12/618,500 filed Nov. 13, 2009, which claims thebenefit of U.S. provisional application No. 61/114,855 filed Nov. 14,2008. The entire disclosure of each prior application is expresslyincorporated herein by reference thereto.

FIELD OF THE INVENTION

The invention relates to the fabrication of semiconductor structures,and in particular to the epitaxial growth of high crystal qualitystructures comprising III-nitride materials. Embodiments of theinvention include methods for improving the crystal quality of asemiconductor structure, and structures fabricated utilizing thesemethods.

BACKGROUND OF THE INVENTION

The quality of a semiconductor material can considerably influence theperformance of a solid-state device produced from said material.Solid-state devices can suffer from inferior lifetimes and operatingcharacteristics when the semiconductor material has an undesirabledensity of crystal defects, for example dislocations. Such problems havehindered the development of semiconductors including gallium nitride(GaN), other Group III-nitrides (e.g., AlN, InN, GaInN) and other mixednitrides (referred to herein as “III-nitrides”) as well as certain GroupIII-V compounds; and of certain other compound materials (e.g., IV,II-VI materials) generally. For many of these materials suitable andcommercially useful growth substrates have limited availability and poorcrystal quality. A suitable substrate closely matches the crystalproperties of the target material to be grown; if these properties donot closely match, the resulting material usually has an unacceptabledensity of dislocations.

Specifically, in the case of GaN, crystal quality can be improved bypre-treatment of the growth substrates, e.g., by nitridization and otherchemical modifications; by growing thin, low temperature buffer layersof other III nitrides, e.g., AlN or GaN, by thermal annealing, and thelike. Methods such as epitaxial lateral overgrowth (ELO) and itsvariants (PENDEO, FIELO, etc) have proven successful in reducingdislocation density. However, these common methods often utilizelithographically produced masking elements that often produce materialswith a non-uniform distribution of surface dislocations, undesirable inmany applications. Some alternative methods of dislocation reduction forproducing homogenous surface dislocation densities have utilized in-situ(or ex-situ) deposition methods to impede dislocation progression, insome instances with the addition of etchants to enhance surfacedislocation dimensions. Examples of such impeding methods include USpatent publication U.S. 2007/0259504, Tanaka et al. Japanese Journal ofApplied Physics 39 L831 2000 and Zang et al. Journal of Applied Physics101 093502 2007. Further alternative methods of dislocation reductionaim to limit dislocation propagation into the growing layer by, at anintermediate stage of growth of a GaN layer, enhancing defects presentat the surface of the GaN layer by etching, then plugging plugging theenhanced surface defects with a masking material on which GaN does notreadily nucleate, and then continuing GaN growth. Examples of suchmethods include US provisional patent application 61/127,720 filed May14, 2008, which is incorporated herein by reference in its entirety.

Layers and crystals of III-nitrides of improved quality are desirable.Although applicable processes for doing so are available in the priorart and succeed to a certain degree in reducing the dislocation densityin III-nitride materials, a method capable of producing greaterdislocation reduction and uniformity of distribution is desirable.

SUMMARY OF THE INVENTION

The present invention provides systems and methods for fabricatingsemiconductor structures and in particular fabricating semiconductorstructures comprising III-nitride materials. Methods of the inventioncan fabricate semiconductor layers with improved crystal qualities, e.g.with fewer dislocations, in comparison to the state of the art. Theinvention also provides semiconductor structures fabricated by thesemethods.

Generally, methods of the present invention produce better-quality,following semiconductor layers (or “final” or “overlying” or “overgrown” layers, or the like) by taking advantage of certain types ofdislocations commonly found in poorer-quality starting layers (or“substrates”, “initial” or “underlying” layers, or the like).

It has been found that, up to a point, the more prominent the surfaceextent of dislocations in a starting or underlying surface, the betterthe quality of a following layer ultimately fabricated from such astarting or underlying surface. It is believed (but without intendedlimitation) that this surprising outcome results from the interplay of anumber of factors.

First, the dislocations in an underlying semiconductor surface may beenclosed and terminated, in such a manner, and a final layer can begrown in such a manner, that the terminated dislocations do notpropagate into the final layer. The final layer can then have fewerdislocations than the underlying surface because those dislocations inthe underlying surface that have been successfully enclosed andterminated are not represented in the final layer. Second, it has beenfound that the common surface indentation (e.g. a pit like structure)spontaneously produced at dislocations in an underlying surface can beenhanced, e.g., made larger in surface cross section (e.g. increased insize for both lateral and depth dimensions), such that they can be moreeffectively terminate associated dislocations when compared with lessenhanced dislocations. Finally, it has been found that conditionsencouraging the intersection of two or more enhanced dislocationsfurther enhances the termination of associated dislocations and thusincreases both the dislocation termination efficiency and the efficiencyof dislocation reduction. Accordingly, a final layer grown from anunderlying surface having enhanced and enclosed dislocations can thenhave even fewer dislocations than the underlying layer.

Briefly, beginning with an underlying surface of a suitablesemiconductor material, methods of the invention fabricate a followinglayer of improved quality by steps comprising enhancing the commonsurface indentation spontaneously produced at selected dislocationspresent at the underlying surface. Subsequent processes then grow afollowing layer having few or no dislocations arising from the enhanceddislocations in the underlying surface.

In embodiments of the invention, an advantageous method of enhancing thecommon surface indentation spontaneously produced at dislocationscomprises growing an intermediate layer (or layers) having enhancedopenings induced by some or all of the dislocations in an underlyingsurface and grown in a manner such that the induced openings becomeprogressively enhanced as the intermediate layer grows. Additionalembodiments of the invention promote the intersection of two or moresuch enhanced dislocations to a produce an agglomeration (or“clustering” or “bunching”) of enhanced dislocations as the intermediatelayer (or agglomeration layer) grows.

Enhancing surface indentations (e.g. pit like structures) spontaneouslyproduced at dislocation emergences includes enlarging their sizes (e.g.depth, width, and surface cross section). Enhancing can occur as theintermediate layer grows in thickness. Such enhancing is also referredto as “opening” of dislocations, i.e., the intermediate layer is grownunder conditions so as to “open” dislocations.

A preferred way to achieve the enhancing is by etching the semiconductorsurface under first etch conditions selected to encourage etchingassociated with the surface dislocations, and then forming anintermediate semiconductor layer under first epitaxial growth conditionsselected to encourage opening of growth pits associated with the etchedsurface dislocations.

The intermediate layer is also grown in such a manner that the enlargingof the common surface indentations spontaneously produced atdislocations results in the intersection of two or more such surfaceopenings. Such intersecting of two or more openings (or pits) isreferred to as pit “agglomeration” or pit “clustering”, i.e. theintermediate layer is grown under conditions so as to “open” therelevant types of dislocations the “openings” intersecting one or moreother “openings” to form an agglomeration or clustering of openings.

In additional embodiments of the invention, a further advantageousmethod of enhancing dislocations includes treating the surface withetching agents selected to encourage the enlarging of the dislocationpits, i.e. to open (or to “decorate”) the natural indentations found atthe surface of the underlying material to form “etch pits”. As withgrowth of an intermediate layer, enhancing can occur as the etchingprocess proceeds thereby “deepening” and “opening” of dislocations so asto produce “open” dislocations. Proper etching conditions can also leadto intersection of two or more such surface openings or disturbancesabout the surface emergences of bulk dislocations producing pit“agglomerations” or pit “clusterings” similar to those produced in anintermediate layer.

Finally, an advantageous method of terminating the dislocationscomprises laterally growing over or from within the agglomeration ofopenings, induced by the dislocations, with a lateral growth layer. Thelateral growth layer can comprise materials (e.g., III-nitridematerials) selected to have crystalline properties substantially similarto those of the underlying layers. This growth step begins underconditions selected to promote such lateral growth, and continues, ifnecessary, under condition selected to promote more vertical growthuntil a desired layer thickness has been reached.

In preferred embodiments, prior to terminating the dislocations, theinvention includes depositing a discontinuous film of a dielectricmaterial, such as a silicon nitride or oxide in the case of aIII-nitride semiconductor. By choice of appropriate deposition (and/orpost deposition conditions), it has been found that the dielectricmaterial deposits discontinuously so as to reduce the number ofdislocations in the laterally growing material. It is believed that thisis because the discontinuous deposition occurs in the disordered regionsabout emergent dislocations so as to discourage subsequent lateralgrowth from more disordered regions about the emergent dislocations(which would promote the propagation of dislocations into the growingmaterial) and to encourage subsequent lateral growth from lessdisordered regions about dislocations (which hinders the propagation ofdislocations into the laterally growing material).

The invention also includes performance of the above steps in variouscombinations and orders. For example, surface-emergent dislocations canbe enhanced by careful growth of an intermediate layer on an initialsurface, or by careful etching of the initial surface, or by growth ofan intermediate layer followed by careful etching, or by etchingfollowed by growth of an intermediate layer (optionally followed by afurther careful etching). Lastly, a following layer with reduceddislocations is grown laterally following careful deposition of adiscontinuous layer of a dielectric material.

The invention is usefully applied to those (“suitable”) semiconductormaterials in which occur types of dislocations that can be efficientlyand reliably enclosed e.g., by enhancement and then lateral growth, andwhich can be grown by processes such that enclosed dislocations in anunderlying surface induce few or no dislocations in an overlying layer.The types of dislocations selected for enclosure by the invention candiffer among different suitable semiconductor materials, as can methodsof enclosing dislocations of the selected types and methods of growingthe material over surfaces with processed dislocations.

Semiconductor materials comprising III-nitrides, and especiallymaterials comprising GaN, have been found to be particularly suitablematerials. Accordingly, the following description is largely directed tosuch embodiments that fabricate layers comprising III-nitride materials.However, it should be understood that the present invention is notlimited to III-nitride materials, and can usefully be applied to othermaterials.

The present invention provides both methods for fabricatingsemiconductor structures and the semiconductor structures fabricated bythe provided methods. In more detail, these methods include epitaxiallygrowing a layer of semiconductor material on an initial semiconductorsurface with a plurality of emergent surface dislocations, that firstforms an intermediate semiconductor layer having growth pits andagglomerations of growth pits by epitaxial growth on the initial surfaceunder first epitaxial growth conditions selected to encourage opening ofgrowth pits associated with the surface dislocations, and thensubsequently under second epitaxial growth conditions selected toencourage intersection of two or more growth pits into agglomerations ofgrowth pits, and then second forms a substantially continuous followingsemiconductor layer having fewer surface dislocations than the initialsemiconductor surface by epitaxial growth on the intermediate layerunder third epitaxial growth conditions selected to encourage lateralgrowth over or from within some or all of the growth pits and theagglomerations of growth pits.

The methods of the invention also include forming a III-nitridesemiconductor structure, the semiconductor structure having an initialIII-nitride surface with a plurality of emergent dislocations, thatepitaxially grows following III-nitride semiconductor layer under asequence of growth conditions selected so as to encourage, first,opening of growth pits associated with the surface dislocations, thensecond, intersection of two or more of the opened growth pits intoagglomerations of growth pits, and third lateral growth over or fromwithin some or all of the growth pits and the agglomerations of growthpits at least until formation of a substantially continuous layer,wherein the dislocation density in the substantially continuous layer isless than the dislocation density on the initial surface.

Also, the sequence of growth conditions can be entirely carried out in asingle growth chamber without removal of the III-nitride semiconductorstructure from the growth chamber, and further, repeating the sequenceof growth conditions without removal of the III-nitride layer beingformed from the growth chamber. The opening and intersection of growthpits continues preferably as long as a plurality of individual growthpits have lateral extents of less than about 5 μm. Also, the growth pitsare preferably formed by etching the III-nitride surface under firstetch conditions selected to encourage etching associated with thesurface dislocations.

Aspects of these methods include repeating the steps of forming theintermediate layer and of forming the substantially continuous followinglayer two or more times; prior to forming the intermediate semiconductorlayer; prior to forming the substantially continuous followingsemiconductor layer; and applying a discontinuous layer of a dielectricmasking material to the intermediate layer.

Aspects of the methods also include growth condition for encouraging theopening of growth pits and for encouraging the intersection of growthpits that are substantially similar; growth conditions for encouragingthe opening and intersection of growth pits comprise temperatures ofless than 1000° C., pressures of greater than about 100 mb, or both.

The present invention also provides a III-nitride semiconductorstructure having a first layer having a plurality of defects propagatingwithin the layer and a plurality of voids, each void associated with oneof more of the propagating defects; and a substantially continuousfollowing layer overlying lateral overgrowth layer with substantially novoids and having fewer propagating defects than in the first layer.

This structure can have a plurality of the voids have a narrower apexwithin the first layer at which at least one defect terminates, and havebroader bases adjacent to the boundary with the following layer; aplurality of pairs of a first layer and a following layer, each pairdirectly overlying a previous pair; dislocations emerging at the surfaceof the following layer are distributed substantially uniformly over thesurface; one or both of the intermediate layer and of the followinglayer with thicknesses of between about 0.1 μm and 1.5 μm and preferablyless than about 1 μm.

In particular, the structure is a Group III-nitride semiconductorstructure comprising a first layer having a surface and agglomerationsof growth pits located beneath the surface in the structure in place ofpropagating defects, wherein the growth pits present voided regions thatgradually increase in size towards the surface of the first layer, andhave one or more sides that are at least partially covered with maskingmaterial to prevent growth of semiconductor material on the partiallycovered side(s).

The term “substantially” is used herein to refer to a result that iscomplete except for the deficiencies normally expected in the art. Forexample, an epitaxial layer cannot routinely be expected to becompletely continuous (or completely monocrystalline, or completely ofone crystal polarity) across macroscopic dimensions. However, anepitaxial layer can routinely be expected to be “substantiallycontinuous” (or “substantially monocrystalline”, or “substantially ofone crystal polarity”) across macroscopic dimensions where thediscontinuities (or crystal domains, or crystal boundaries) present arethose expected in the art for the processing conditions, the materialquality sought, or so forth.

Further, a semiconductor layer having “substantially no dislocations” isused herein to mean that the semiconductor layer has a density ofdislocations that is at least low or a very low in comparison to what iscommon in the art for the material of the semiconductor layer. Forexample, in the case of GaN, “substantially no dislocations” (or a lowor very low density of dislocations) is taken to refer to herein todislocation densities of less than approximately on the order of10⁶/cm², and especially less than approximately on the order of 10⁵/cm². The dislocation density in the group III nitrides is measured bymethods well know to those familiar in the art, including, atomic forcemicroscopy, optical microscopy, scanning electron microscopy andtransmission electron microscopy. The preferred method for measuring thedislocation density is by transmission electron microscopy (TEM).

Headings are used herein for clarity only and without any intendedlimitation. A number of references are cited herein, the entiredisclosures of which are incorporated herein, in their entirety, byreference for all purposes. Further, none of the cited references,regardless of how characterized above, is admitted as prior to theinvention of the subject matter claimed herein. Further aspects anddetails and alternate combinations of the elements of this inventionwill be apparent from the following detailed description and are alsowithin the scope of the inventor's invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention may be more fully understood by reference to thefollowing detailed description of the embodiments of the invention,illustrative examples of specific embodiments of the invention and theappended figures in which:

FIGS. 1A, 1B, 1C, and 1D schematically illustrate an embodiment of theinvention;

FIG. 1B b illustrates a further alternative embodiment;

FIG. 2 schematically illustrates growth pits and agglomerated growth pitstructure produced by embodiments of the invention;

FIGS. 3A, 3B, 3C, 3D, and 3E schematically illustrates a furtherembodiment of the invention;

FIGS. 4A, 4B, 4C, 4D, 4E schematically illustrates a further embodimentof the invention;

FIGS. 5A, 5B, 5C, and 5D schematically illustrate the repeated use ofembodiments of the invention;

FIGS. 6A and 6B illustrate practical examples of embodiments of theinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Although the following description is predominantly directed towardsembodiments that fabricate layers comprising III-nitride materials, itshould be understood that embodiments are not limited to such materials.Therefore, without limitation, embodiments of the inventionsubstantially prevent dislocations that are present at a surface layerof a semiconductor structure from being present at a following surfacelayer of the structure, such that the following surface of the structurecan have improved quality. These methods can be performed once toimprove the quality of the following layer, or can be performed two ormore times to successively improve the quality of successive followinglayers.

Briefly, beginning with an underlying surface comprising a III-nitride(or other) material, methods of the invention grow a following (or“final”) layer of improved quality. The steps comprise enhancing thesurface extent (i.e. width and depth) of the dislocations alreadypresent at the underlying surface, forming agglomerations of enhanceddislocations by promoting the intersection of enhanced dislocations, andthen enclosing the enhanced dislocations by growing over or within theagglomerations of enhanced dislocations with a following layer ofmaterial having few or no dislocations.

In embodiments of the invention directed to III-nitride materials,dislocations are enhanced preferably by epitaxially growing, anintermediate layer (or layers) of a same or different III-nitridematerial. The intermediate layer(s) include growth pits associated withalready-present, surface dislocations in an underlying III-nitridesurface and are induced by and at the locations of some or all of thedislocations in the underlying.

The intermediate layer is grown so that the surface openings (e.g. thewidth and depth) of the growth pits gradually increase, in other words,so that the growth pits open. Growth pits usually have aninverted-pyramid-type form, so that during growth of the intermediatelayer, the growth pits tend to naturally broaden and deepen and becomeprogressively enhanced (“open”) as the thickness of the intermediatelayer increases. All or substantially all of the growth pits include adislocation located at the apex of the inverted pyramid type structure.Therefore, upon opening of the growth pit the originating dislocation isproximate to a voided region produced by the growth pit.

In addition to promoting the opening of growth pits, the underlyinglayer and the intermediate layer are formed in such a way so as topromote the intersection of two or more growth pits, such that thecombined surface opening of the intersecting growth pits increases asthe total lateral extent of the surface opening in the intermediatelayer. A group (two or more) of intersecting growth pits is referred toherein as an “agglomeration” or “pit agglomeration”, and the surfaceopening of a pit agglomeration is referred to as an “agglomerationarea”. The surface of the intermediate layer therefore comprises aplurality of agglomeration areas produced by the intersection of two ormore growth pits. An agglomeration area comprises a number dislocationslocated at the base of the area (i.e. the apex of the individualinverted pyramids) and an expansive voided region resulting from thecombined internal voided volumes of the intersecting growth pits.Thereby, the surface openings of growth pits can be enhanced or evengreatly enhanced.

It can be appreciated, therefore, that according to the invention afirst step in producing a layer of increased quality is to produce anintermediate layer comprising a plurality of intersecting growth pitsthat form a plurality of pit agglomerations. Such an intermediate layerhaving enhanced agglomerated growth pits is also referred to herein as a“pitted” layer.

In further embodiments of the invention an additional step comprisestreating (preferably by etching) an underlying surface to particularlyencourage positioning of enhanced dislocations (i.e. growth pits) in anintermediate layer at dislocations present in the underlying surface.Such an etching step can occur preferably before growth of anintermediate layer, but can also occur after growth of the intermediatelayer, and can even be performed alone without growth of an intermediatelayer.

For example, when the semiconductor is GaN, the etching is preferablyconducted with aqueous KOH at a temperature of from 75 to 90° C. for atime of between 1 and 30 minutes, with molten KOH at a temperature of250 to 300° C. for a time of between 1 and 10 minutes or with SiH₄ at atemperature of from 800 to 925° C. for a time of between 1 and 10minutes with the higher temperatures in the range requiring shortertimes than the lower temperatures. Other etchant and processing timecombinations can be used depending upon the specific semiconductormaterial that is used.

Also, the etching can be enhanced in a number of ways. The mostconvenient way to do this is to adjust the temperature and etching timeas necessary to achieve the desired result. The etching can be conductedto open the pits to facilitate the introduction of the amorphousmaterial therein but to not be so aggressive that the surface of thesemiconductor material is removed to minimize the size of the pits. Ifetching is insufficient, the temperature or time can be increased. Incertain applications, the simultaneous addition of laser or UV energycan be used to enhance etching.

Once formed the agglomerated growth pit openings induced viadislocations in the underlying surface layer are enclosed and coveredwith a continuous uniform following layer of III-nitride. The sizes ofthe agglomerated areas of the growth pits are therefore preferablyadjusted by, e.g., the thickness of the intermediate layer, density ofdefects in the initial layer, the growth condition etc., so that thesurface extent of the intersecting growth pit openings are sufficientlysized so that ELO processes bridge (or span) a multitude of dislocationsproducing a continuous surface.

In other words, the intermediate layer is grown so as to open andintersect a plurality of growth pits to produce surface opening with asize suitable to cluster a plurality of dislocations at the base of theenhanced pit opening. Therefore, subsequent lateral growth of afollowing III-nitride layer encloses the enhanced surface openingpreventing further propagation of the underlying dislocations.

The surface distribution of dislocations across a final surface will besubstantially uniform (up to statistical fluctuations) if thedistribution of dislocations across an initial surface is similarlyuniform. This is because the steps of the invention randomly reduce thenumber of initial dislocations without significant, if any, surfacebias. Therefore, as the number of initial dislocations is reduced, theirdistribution is largely preserved. For example, the random distributionof dislocations present at an initial surface will be enhanced duringsubsequent growth of an intermediate layer thereon (or surface etching),and the random distribution of the enhanced dislocations present at thesurface of an intermediate layer (or etched initial layer) willsuccessfully be enclosed during subsequent dislocation processing.Accordingly, if a random surface distribution of dislocations isdesirable, it is preferable to start with an initial surface also havinga random surface distribution of dislocations.

The invention also includes III-nitride semiconductor structuresproduced by the above methods. Such structures have observable evidenceof such enhanced and intersecting growth pits and dislocations arrangedin planes representing the surfaces of the intermediate layers in whichthey were formed.

More detailed descriptions of various embodiments of the invention arenow presented, beginning with the embodiments of FIGS. 1A-D. Thesefigures illustrate the principal features of preferred embodiments in aschematic manner. In particular, these figures are not to scale,illustrate exemplary dislocations, and are not representative of theactual performance of this invention in improving quality. It shouldalso be noted that although much of the following description of thepreferred embodiments of the invention are specific to gallium nitridelayers, this should not be construed as limiting the invention to saidmaterial but encompasses the whole family of the III-nitride and othersemiconductor materials.

FIG. 1A illustrates an initial gallium nitride semiconductor layer thathas been epitaxially grown (or otherwise placed or transferred) on asubstrate and that has dislocations emerging at its surface. FIG. 1Billustrates the results of a first step of a preferred embodiment thatproduces an intermediate layer with a surface including a plurality ofintersecting “pits” (or intersecting hollows, cavities, depressions etc)(equivalently, a “pitted intermediate” layer, or “pitted” layer, or thelike). The intersecting pits (equivalently, agglomerated or clusteredareas of “growth” pits) of the “pitted” layer are induced by all or asubstantial number of the dislocations present at the surface of theinitial gallium nitride layer. The intersection of a number of growthpits produces extend voided regions with a number of dislocationslocated primarily at the base of the regions.

FIG. 1B b illustrates a preferred embodiment in which a dielectric layerof material is deposited to assist in dislocation reduction; suchmethods of the invention are described later in greater detail. In thisembodiment, a thin layer of masking material 131 is applied to thesurface of the pitted intermediate layer 120 preferably in a manner sothat a portion of side facets of the growth pits and agglomerated growthpits (preferably the more disordered portions) are covered while leavingthe remaining portions (preferably the less disordered portions) and theunpitted planar material accessible for subsequent material growth.Preferred masking materials comprise substances which act asanti-surfactants to III nitride growth, thereby limiting the amount ofnucleation in masked portions of the structure of FIG. 1B b.

FIGS. 1C-D illustrate overgrowth of a following III-nitride layer on theupper surface of the pitted intermediate layer according to epitaxiallateral overgrowth as is known in the art. During the overgrowth processthe material of the following layer epitaxially overgrows and enclosesthe extended voided regions formed via intersecting growth pits therebysealing portions of the pits, terminating dislocations located at thebases of the agglomerated growth pits, and preventing their propagationinto further III-nitride material thereby being prevented. The epitaxialgrowth is continued until the material of the following layer coalesces,forming a substantially continuous film, at which point the growth modecan be altered to promote growth of a more vertical growth for producingmaterial to a desired thickness in more effective manner.

All or substantially all of the growth-pits of the pitted layeroriginate from or are induced by emerging dislocations in an underlyinginitial III-nitride layer. Therefore, when enclosed, the dislocationscannot continue (or propagate) into a following epitaxial III-nitridelayer grown on the pitted layer. Because the following layer grows, atleast initially, above and over the agglomerated growth pits viaepitaxial lateral overgrowth (ELO), the dislocations are unable toinduce dislocations into the following layer. In preferred embodiments,the material of the following layer is substantially the same as, or hascrystal properties very closely similar to, the semiconductor materialof the intermediate pitted layer, so that the interface between theselayers will induce few or no dislocations or dislocations in thefollowing layer. Thereby, in embodiments of the invention, the followinglayer has improved quality in that it has fewer dislocations than arepresent at an initial surface.

The particular embodiment illustrated by FIGS. 1B (and 1Bb), 1C, and 1Dtherefore proceeds by producing a pitted layer with a plurality ofintersecting pits, e.g., an intermediate layer with suitably enhanced(e.g., sufficiently open) pit agglomeration areas or regions,originating at all or substantially all of the surface dislocations ofthe underlying initial layer, then sealing portions of the pittedsurface by lateral over growth of a following layer of III-nitridematerial.

In more detail, FIG. 1A illustrates an initial III-nitride layer 100(e.g., gallium nitride) grown on substrate 102 during an initialepitaxial process (or otherwise placed on substrate 102, e.g., by layertransfer). In addition, the combination of layers 100 and 102 couldconstitute a single layer of material such as a free standing GaN or Siwafer). Dislocations, represented at 104, 106 and 108, can arise atinterface 110 between the initial layer and the substrate, often becausethe crystal properties (and other physical properties) of the initiallayer material do not sufficiently closely match those of the materialof substrate 102 (or the substrate on which layer 100 is grown). Thesedislocations can continue (or “propagate”) along with the growingmaterial into initial layer 100 and disturb the crystal structure as thedislocation intercepts the growing layer surface.

For example, dislocations 104 emerge as surface dislocation 112 wherethe structure of the surface is more significantly disturbed (incomparison to a defect-free portion of the surface). In comparisondislocation 106 emerges as surface dislocation 116 with little to noobvious disturbance of the surface. For example and not to be limited bytheory, the significance of the surface disturbance resulting from theemergence of a dislocation at the growing surface can, in certain cases,be dependent on the characteristics of the dislocation e.g. strain,Burgers vector, nature i.e. screw, edge, mixed type etc. (see forexample Hino et al. Applied Physics Letters 76 3421 2000). In the caseof GaN, dislocations 104, 106 and 108, are most commonly threadingdislocations (TD), and can be numerous in layers epitaxially grown onsapphire substrates. Dislocation 106 can also arise in the bulk of thegrowing III-nitride material and continue or propagate along with thegrowing layer to emerge 116 at initial layer surface 118. These types ofdislocations typically less significantly disturb the surface. It shouldbe noted that any defect, however originated, can emerge with greater orlesser surface disturbance. A greater disturbance can include, asillustrated by emergence 112, depressions, or hollows, or the like, thatare apparent on unaided examination. A lesser disturbance can include,as illustrated by emergence 116, a less significant surface disturbancecommonly only apparent upon aided examination e.g. via scanning electronmicroscopy (SEM), atomic force microscopy (AFM). It is common practiceto reveal (commonly referred to as “decorating”) such dislocations tomake them more readily apparent, e.g., via an etching process.

A subsequent III-nitride layer (the pitted or intermediate III-nitridesemiconductor layer) 120 is epitaxially grown on the surface of theinitial gallium nitride layer 118. The pitted layer III-nitride layer incertain embodiments has crystal properties, e.g. lattice parameters,thermal expansion coefficient, that are substantially matched to thoseof initial III-nitride layer 100. The matching of crystal propertiesbetween pitted layer 120 and initial layer 100 substantially preservesthe material quality from the initial III-nitride layer to the pittedIII-nitride layer. Since the initial layer can comprise gallium nitridethe pitted layer will substantially preserve the crystal quality of theinitial III-nitride layer, e.g. comparable dislocation density, if ittoo comprises gallium nitride or an alloy thereof.

Pitted III-nitride layer 120 can be epitaxially grown by various methodsincluding hydride (halide) vapor phase epitaxy (HVPE), metallorganicvapor phase epitaxy (MOVPE), and molecular beam epitaxy (MBE). Thedislocation density at initial III-nitride layer surface 118 and thegrowth conditions for pitted layer 120 are optimized in order to promotethe formation and intersection of pit like structures that lead to theagglomerated or clustered growth-pits 122 opening at pitted (e.g.rutted, potholed) surface 126. Dislocation 108 is illustrated asresulting in growth pit structure 124, however growth pit structure 124has not intersected further growth pits and therefore the surfaceopening produced at surface 126 is less significant than that producedby the clustered or agglomerated region 122.

The density of dislocations in the initial layer surface 118, and thegrowth time (or equivalently the thickness of the intermediate layer)are selected so that the surface emergences of the agglomerated growthpits are suitable sized to be reliably and effectively overgrown. Inaddition the agglomerated growth pits are grown in such a way so as toinclude a plurality of dislocations at their base regions arising fromthe intersecting growth pits. For example, agglomerated growth pitstructure 122 comprises six separate dislocations.

Therefore pitted layer 120 comprises an upper substantially planarsurface parallel to the underlying substrate 102 composed of highquality gallium nitride 128 interspersed with interconnected growth-pitfeatures 122 (voids, depressions etc.). For example, it has been foundthat suitably opened intersecting growth pits are usually formed inpitted (intermediate) layers having thicknesses between 0.1 μm and 1.0μm.

In addition, in certain embodiment it may be advantageous to employ aninitial III-nitride layer which has a significant network of surfacedislocation, thereby promoting the formation of growth pits andincreasing the probability of growth pit intersection. Therefore incertain embodiments of the invention initial III-nitride surface 118 maycomprise a surface dislocation density of greater than 5×10⁷cm⁻², oralternative embodiments a surface dislocation density of greater than1×10⁹ cm⁻² or finally in other alternative embodiments a dislocationdensity of greater than 1×10¹⁰ cm⁻².

It should be appreciated that the intersection of the growth-pits in thepitted intermediate layer leads to agglomerated regions (with two ormore growth pits) having substantially discrete voids extendedintersecting surface openings 122 in surface 126, preferably with asubstantially uniform distribution throughout the pitted layer.Therefore, it is preferred that the original surface dislocations have asubstantially uniform distribution in original surface 118. Thegrowth-pits originate from all or a number of the dislocations presentat surface 118 of the initial III-nitride layer and extend through allor a portion of the pitted intermediate layer. For example, dislocations104 are illustrated as forming surface disturbances 112 (FIG. 1A) whichintersect to form a portion of agglomerated pit structure 122 in layer120.

However, some surface dislocations may not lead to agglomerations. Forexample, dislocation 106 does not form or forms a lesser surfacedisturbance at surface 118 and as such does not induce a growth-pitstructure in pitted layer 120. Dislocation 106 can therefore propagatethrough layer 120 to emerge at surface 126 where it can result in asurface disturbance 130 of lesser or greater significance. In addition,dislocation 108 produces growth pit 124 upon formation of theintermediate layer, however due to process conditions and thedistribution density of dislocations in the initial III-nitride layergrowth pit 124 is not capable of intersecting with other growth pitstructures. Therefore, dislocation 108 forms a single opening 124 atsurface 126 which is reduced in lateral extent compared with thosegrowth pits capable of intersection.

Further, some pit structures may not be directly adjacent to templatesurface 118 but instead can originate from a propagating dislocationwithin layer 120. Such growth-pits therefore may not extend through theentirety of pitted III-nitride layer 120 (this layer refers to all thematerial between surface 126 and surface 118). For example, pitstructure 124 in FIG. 1B originates from propagating dislocation 108within layer 120 so that the apex of this pit structure is not directlyadjacent to surface 118. Although a majority, or substantially all, oreven nearly all of the growth-pits may extend through the entire pittedlayer, it should be understood that some other growth pits may extendonly through a fraction of the pitted layer. Therefore, statementsherein to the effect that growth-pits originate at all or a number ofthe dislocations at surface 118 of the template layer should not to beinterpreted as excluding embodiments in which some growth-pit structuresactually originate within layer 120.

FIG. 2 represents in exemplary fashion a portion of pitted intermediatelayer 120 (delimited by dashed lines) between upper surface 126 andlower surface 118 (which is the upper surface of initial III-nitridelayer 100), and further illustrates individual (non-intersecting)growth-pits and growth-pit clustering or agglomeration as commonlyformed in preferred embodiments of the invention. The individualgrowth-pits commonly take on a hexagonal geometry at the emergence withsurface 126 (when the semiconductor material of the pitted layercomprises a III-nitride which has a hexagonal crystal structure). Anon-intersecting growth pit 124 is illustrated as having an interceptwith surface 126 having a width (W₁) and a depth (D₁) and an invertedpyramid like structure with angled facets 202. Dislocation 204 isillustrated as propagating into pitted layer 120 resulting in theformation of growth-pit structure 124. The depth (D₁) of growth-pit 124is illustrated as encompassing only a portion of pitted layer 120without limitation. Other individual growth-pits can extend through allof the pitted III-nitride layer.

In contrast, the intersecting growth-pits of agglomerated structure 122are illustrated as encompassing the entire depth of pitted III-nitridelayer 120, originating in the initial gallium nitride layer (not shownin this schematic) and emerging at surface 126. The width of thegrowth-pits and growth-pit agglomeration can vary from place to place atthe surface of the pitted layer. Without limitation, it is believed thatthe extent to which the growth-pit extends into current semiconductorlayer is dependent on the characteristics of the dislocationsthemselves, e.g. for dislocations the depth (D) may vary for screw, edgeand mixed type structures and also on the strain and Burgers vector ofthe dislocation, and also that the width of an individual pit opening atsurface 126 is in part dependent on the characteristics of thedislocation that induced the pit, e.g. W may depend on nature ofdislocation type, strain, etc.

Also, the width of growth-pits increase in response to the growththickness of the pitted III-nitride layer. For example, individualgrowth-pit 124 has a width (WO at the intercept with surface 126,however the width of the growth-pit would decrease if the pitted layerthickness decreases. As illustrated in FIG. 2 the width of growth-pit124 at an earlier stage of pitted III-nitride layer growth is given asW′, where as the growth-pit width at a later stage of growth is given asW. It is clear that width W is greater than W′. It is believed withoutlimitation that the increase in pit width is due to the difference insurface energies between the angled pitted facets, typically (000) andthe growth facets parallel to surfaces in relation to the growthmechanism proximate to the growth-pits. In this manner, the pitstructures enhance the surface distortion produced by the emergentdislocations in both a lateral and axial extent. Such expansion of thesurface profile and size of the dislocation (dislocation enhancement)whilst maintaining the high quality of the surrounding gallium nitridecrystal makes it easier to process, e.g., overgrow, so that the surfaceof the following semiconductor layer is improved, i.e., has lessdislocations.

The lateral extent of the growth pits is further increased through theintersection of two or more growth pit structures. Pit agglomeration (orclustered) structure 124 represents the intersection of three individualgrowth pits producing a lateral opening at surface 126 of W₂. Theindividual voided regions of the three growth pit structures combine toform a significantly increased voided region with the three individualdislocations located at the base of the combined voided region.

The growth-pits and agglomerated growth-pits in pitted semiconductorlayer 120 are preferably produced by way of carefully selected growthparameters. In certain embodiments, a low temperature growth of layer120 is found to enhance the formation of pits. In this context lowtemperature growth is defined as a growth temperature less than thatcommonly used for the deposition of high quality III-nitrides (e.g. forgallium nitride approximately 1000-1150° C.). For example, the lowtemperature growth for formation of gallium nitride growth-pits would beon the order of less than 950° C., or on the order of less than 900° C.,or alternatively on the order of less than 850° C. In other embodimentsthe temperature of the growth is maintained at that commonly used forhigh quality film growth (e.g.≈1000 to 1150° C. for gallium nitride) andthe pressure of the growth reactor is increased above that commonlyutilized for high quality III-nitride deposition. For example, forgallium nitride films the growth pressure would be on the order ofgreater than 100 mbar, or on the order of greater than 200 mbar, oralternatively on the order of greater than 300 mbar. In otherembodiments, the doping level of the III-nitride film is varied toenhance the promotion of growth-pits. For example, Son et al. examinedSi doping and the effect on void formation and found pit densitydecreases with Si doping. The growth parameters for promoting theformation of growth-pit like structures may not be independent of oneanother and various combinations of parameters may enhance the formationof the growth-pits in the III-nitride film.

The arrangement and density of the clustered growth-pits should be suchthat, upon sealing portions of the pits, sufficient surface area awayfrom the sealed growth-pits (e.g., surface that is at least free ofsignificant dislocations or disorder) remains for subsequent epitaxialnucleation and for support of the following epitaxial layer. Generally,at least approximately 25% or more of the original area of the surfaceof layer 120 should remain intact and free of agglomerated growth-pitareas, and preferably at least approximately 50% or more, and morepreferably at least approximately 75% or more.

In the further preferred embodiment of the invention, illustrated inFIG. 1B b, a thin layer of masking material 131 is applied to thesurface of the pitted intermediate layer 120 preferably in a manner sothat a portion of side facets of the growth pits and agglomerated growthpits (preferably the more disordered portions) are covered while leavingthe remaining portions (preferably the less disordered portions) and theun-pitted planar material accessible for subsequent material growth.Preferred masking materials comprise substances which act asanti-surfactants to III nitride growth, thereby limiting the amount ofnucleation in masked portions of the structure of FIG. 1B b. Depositionof anti-surfactant materials onto a secondary material changes thesurface growth kinetics by reducing the sticking coefficient (i.e. theprobability of adsorption of a chemical species on a surface). Thereforein the case of the GaN that the anti-surfactant can substantiallypreclude the adsorption and incorporation of Ga onto the anti-surfactantsurface and subsequently prevents the nucleation of GaN. In certainembodiments the anti-surfactant material comprises dielectric materials;examples of such materials comprise silicon oxides, silicon nitrides andmixtures thereof.

In an exemplary preferred embodiment of the invention, silicon nitrideis utilized as a dielectric masking material 131. The silicon nitridecan be formed on the surface of growth pit 124 and agglomerated growthpits 122 employing a number of methods well known in the art, forexample. PVD, MBE, sputter deposition and spin-on coating techniques.However, it is advantageous that the deposition of the dielectricmasking layer be performed in the reactor chamber utilized for theproceeding growth as it is desirable to perform the entire growthprocedure within a single reactor so that a substrate being processed innot exposed to atmosphere (at if ex-situ processing were performed). Theability to exclude ex-situ processing not only simplifies processprotocols but also reduces operational costs due to equipmentsimplifications.

A discontinuous silicon nitride layer can be deposited by CVD processes,e.g., from gaseous silane (SiH₄) and ammonia (NH₃) under conditionsknown in the art. CVD reactors for producing III-nitride materialsfrequently employ NH₃ as a Group V element precursor, thereforedeposition of silicon nitride only requires the additional of a SiH₄input to the reactor chamber, along with any additional auxiliaryfixturing. The growth thickness of the silicon nitride layer 131 ispreferable maintained at a mean value between approximately 5 Å and 30Å, and preferably below approximately preferably 20 Å to further ensurethe discontinuity of the masking layer coverage over the substantiallyplanar portion of the surface of intermediate layer article 120.

During the deposition of the thin, discontinuous layer of siliconnitride, a random deposition is achieved in that the material isdeposited over single unagglomerated growth pits, agglomerated growthpits as well as the planar non-pitted material.

Silicon nitrides and silicon oxides (and other) masking materials areprovided to substantially reduce nucleation and promote lateralovergrowth over the pit structures in order to further promote thereduction of dislocations in the following layer of III-nitridematerial.

After growth of the pitted III-nitride layer, e.g., layer 120 withclustered pit structure 122 and individual pit structure 124, the pitstructures are next sealed (or spanned, bridged etc.). The sealinggrowth step substantially prevents dislocations located at the base ofthe growth pit structures from propagating or inducing further defectsin a following III-nitride material. Therefore, embodiments of theinvention can grow a following III-nitride material with improvedquality, i.e. with a reduced dislocation density. Preferred embodimentsof the invention seal the dislocations located at the base of the pitstructures by over growth of a following layer of III-nitride material.The overgrowth layer can nucleate from the upper high quality non-pittedregions of surface 126 comprising high quality III-nitride material 128and then can grow over the clustered growth pit structures and theirassociated dislocations, thereby sealing the defective material andpreventing further propagation of dislocations.

FIG. 1C illustrates the initial stages of lateral growth of layer 132 ofa following III-nitride material. At least until the growth-pits havebeen overgrown and bridged by layer 132, conditions can be selected topromote ELO as known in the art. For example, see Hiramatsu et atJournal of Physics: Condensed Matter 13 6961 (2001). Subsequentlyconditions can be changed to promote vertical growth. The lateral growthnucleates substantially from the high quality upper planar III-nitridematerial of surface 126 of pitted intermediate layer 128 and lesssignificantly from the faceted regions of the growth pit structures. Thelateral growth process therefore overgrows the facetted pit structuresand produces high quality III-nitride material as the following layerinherits the crystalline quality of the nucleation areas.

In certain embodiments the following III-nitride materials have relevantproperties closely similar to those of the material of the III-nitridepitted layer, so that few if any dislocations will arise at theinterface between layer 120 and following layer 132. Thereby, followinglayer 132 will have better quality, i.e., fewer dislocations, than theinitial layer 100 and pitted layer 120. In many embodiments, thefollowing material of layer 132 is substantially the same as the pittedlayer material of 120, for example if the pitted layer comprises galliumnitride then the following layer may comprise gallium nitride or analloy of gallium nitride.

Lateral overgrowth of following layer 132 is continued until acontinuous layer of material is produced, as illustrated in FIG. 1D. Inmore detail, dislocations 104 do not continue into layer 132 becausethey emerge in agglomerated growth pits which have been overgrown andsealed by the overgrowth of III-nitride layer 132. The size andseparation of the agglomerated growth-pits are optimized to facilitatehigh quality ELO growth, i.e. the separation between ELO growth frontsis maintained at a level to prevent dislocation formation uponcoalescence (often due to tilt and twist in the crystal). The ELO growthis illustrated in FIG. 1C where the lateral growth has producedsubstantially isolated regions of material of the following III-nitridelayer, the high quality substantially dislocation free semiconductormaterial of the pitted layer acting as seed portions for growth. Uponcontinued lateral growth, the material of the following III-nitridelayer coalesces to form a continuous layer. FIG. 1D illustrates that thecontinuous following layer has substantially fewer dislocations comparedwith the initial layer 100 and pitted layer 118. Although most orsubstantially all dislocations are sealed, some dislocations, e.g.,dislocation 106, can propagate into the following layer. Dislocation 106extends through initial layer 100 into layer 118 since the initiallateral extent of the surface opening produced by defect 106 wasinsufficient to induce a growth pit (as shown in FIGS. 1B and 1B b).Defect 106 is therefore capable of further propagation in the followinglayer 132 to produce emergent surface defect opening 130.

Dislocation 108 produced growth pit structure 124 that did not interceptother growth pit structures. Generally, the lateral growth over theisolated growth pit does not produce a further dislocation uponcoalescence as shown in FIG. 1D. However, in certain circumstances (asshown by inset 133), during lateral growth over isolated growth pit 124coalescence in the following layer, further dislocation 108 a may beproduced that is emergent at dislocation 134. Dislocations 104 producean agglomerated pit structure, which upon overgrowth forms extend voidedregion 136. Dislocations 104 associated with the agglomerated pitstructure are unable to propagate through the voided region and aretherefore terminated within the intermediate layer unable to producefurther dislocations in the following III-nitride layer.

In certain embodiments upon coalescence, the thickness of the followingIII-nitride layer 132 is increased until a desired thickness is achieved(not shown). In greater detail, the following layer is, as stated,formed by lateral overgrowth to produce a continuous film. Uponcoalescence of the following film 132, a more three dimensional growthmode can be encouraged in order to produce the desired thickness ofmaterial of layer more effectively.

Additional preferred embodiments of the invention are now described. Afirst additional embodiment, described with reference to FIGS. 3A-E, issimilar to the above embodiment except that an etching step is performedprior to growth of the pitted intermediate layer. A second additionalembodiment, described with reference to FIGS. 5A-D, comprises repeatingan embodiment of the invention (e.g., the embodiment of FIGS. 1A-D, theembodiment of FIGS. 3A-E) so that the quality of the final layer is evenmore improved. For brevity, the steps of these additional embodimentsthat are closely related to corresponding steps of the previouslydescribed embodiments are only briefly described. Also, elements ofFIGS. 3A-E and 4A-E that are closely similar to corresponding elementsof FIGS. 1A-D are identified with the same reference numbers.

Turning now to an additional preferred embodiment illustrated by FIGS.3A-E and particularly to FIG. 3A, an initial III-nitride layer 100 (e.g.gallium nitride) is formed on a suitable substrate 102 (e.g. sapphire).The initial layer 100 includes a plurality of dislocations 104, 106 and108 due to dissimilarities between the materials of the initial layerand the substrate (FIG. 3A). The dislocations of the initial layerintersect surface 118 resulting in various degrees of surfacedisturbance depending on the characteristic of the individualdislocations/dislocations. As seen in the previously describedembodiment, dislocation 106 produces little or no disturbance at surface118.

In methods of this embodiment, the surface of the initial III-nitridelayer 118 is subjected to an etching process prior to growth of thepitted intermediate layer. The etching process acts to enhance thelateral extent of surface dislocations of the initial layer to a degreeprior to their enhancement by growth of the pitted layer. Such etchingis said to “decorate” the surface dislocations of the initial layer byincreasing the extent of the surface disturbances produced by all orsubstantially all of the dislocation emerging at surface 118 of theinitial layer 100. The increased extent of the surface disturbances dueto etching significantly increases the probability that thosedislocation producing little or no surface disturbance (e.g. dislocation106) in the absence of etching, in fact, induce growth pits in thesubsequently growth pitted layer thereby further increasing theprobability of a plurality of growth-pits intersecting to form a pitagglomeration region. In this way, additional dislocations emergent atsurface 118 (e.g., those having surface emergences that little disturbthe crystal structure of the surface in the absence of etching) inducegrowth-pit features in pitted layer 120, increase the probability ofgrowth pit agglomeration and are thereby prevented from propagating intoa final layer, which can therefore be of increased quality.

Such selective etching is now described in greater detail with referenceto FIG. 3B. The “decoration” (also referred to as “dislocationvisualization”) step, proceeds by increasing the extents of surfacedisturbances of emerging dislocations by forming cavities in the initialsurface 118 at, or proximate to, the dislocations. The surface ofinitial layer 110 is etched under conditions so that the material oflayer 110 (the “initial” material) is removed primarily or exclusivelyat or in the vicinity of surface dislocations (or other disorderedregions), but is removed little, if at all, from the defect-freeportions of the surface. Cavities (or recesses or depressions) 300, 302and 304 are thereby formed at the locations of most or all ofdislocations on the surface of layer 110. It is preferable thatdislocation etching conditions be selected so that resulting etchcavities are shaped, sized, and arranged so as to have polygonal,circular or oval openings with generally conical or cylindrical shapesthat extend down along the principal axis of the dislocation, generallygradually narrowing with depth from their widest portions at thesurface.

Etchants (e.g., etching solutions) are known in the art that etchsurfaces preferentially at regions of disorder, and less “powerful”versions of these etchants can be used for this etching step. Forexample, less powerful versions are less acidic, or less basic, or lessoxidizing, or the like, than their usual forms. In the specific exampleof gallium nitride, dislocation selective etching can be performedeither in-situ, within a growth reactor, or ex-situ upon removal of thematerial from the deposition reactor. Plasma, photo assisted, wetchemical and vapor phase etching are all methods that can be utilized. Amultitude of etch chemistries can be employed e.g. commonly utilizedchemistries include halogens (e.g. hydrogen fluoride, hydrogen chloride,hydrogen bromide and hydrogen iodide), KOH, NaOH, sulfuric andphosphoric acids. For example etching can be conducted with liquid KOHat temperatures of from 75 to 90° C. or molten KOH at temperatures offrom 250 to 300° C. for a sufficient time to etch and open the pits. Thetime periods can range from 1 to 30 minutes, and in particular from 1 to10 minutes. Preferably, the selective dislocation etching is performedin-situ at high temperature for 1 to 10 minutes, with gases comprisingsilane (e.g., SiH₄) at temperatures of above 800° C. to 1100° C.utilizing vapor phase etching. In-situ etching processes are preferredbecause they reduce the cost and time of the etching step (e.g., loadingand unloading of CVD reactor is avoided).

It should be noted that portions of surface 118 that are less disorderedmay be visualized less significantly by etching than is otherwiseachieved at portions that are more disordered. For example, see PhysicaStatus Solidi (B) 228 395 (2001). FIG. 3B illustrates more significantetch cavities 300 formed at the more disordered surface regions 112(FIG. 3A) that are at, or proximate to, the emergence ofdislocations/dislocations 104 (these dislocations in turn originating atinterface 110 with substrate 102), and less significant cavity 302formed at less disordered surface region 116 that is at, or proximateto, the emergence of dislocation 106. Because of the etching step evenless significant dislocations now induce growth pits in the followingpitted layer and therefore increase the probability of pitagglomeration, whereas without etching, they would have induced adislocation that could propagate through the pitted layer and into afinal layer.

Upon completion of the etch step, this embodiment can proceedsubstantially as previously described. In this case, a pitted layer 120(e.g. comprising gallium nitride) is grown from the selectively etchedinitial III-nitride layer, the pitted layer comprising a planar surfacewith high quality material and a agglomerated pit structure 306.However, FIG. 3C illustrates that dislocation 106 now produces a growthpit structure as a consequence of the dislocation selective etchprocess, whereas previously no such pit-like feature was produced(compare FIG. 3C with FIGS. 1B or 1Bb). The additional growth pitproduced by defect 106 due to the defect decoration process thereforeincreases the lateral extent of the pit agglomeration region produced asthe increased lateral extent of the all the dislocation produces asingle agglomerated pit 306.

Alternatively, the surface of the intermediate layer just-grown on theetched initial surface can further be etched. In a further alternative,the intermediate layer can be grown on an un-etched initial surface (asin the embodiment of FIGS. 1A-D), but the surface of the intermediatelayer can then be etched. And in a still further alternative, the etchstep can be controlled so that the dislocations are sufficientlyenhanced so that growth of an intermediate layer can be skipped.

Finally, regardless of the order of etching and intermediate layergrowth, FIGS. 3D-E illustrate that a III-nitride layer is grown underELO conditions so that it preferentially nucleates on the high qualityIII-nitride material bordering the agglomerated growth pit structure306, but nucleates rarely if at all on the facetted regions of theagglomerated growth pit itself (FIG. 3D). Islands of III-nitride growth308 form on surface 126 and first grow laterally over the agglomeratedgrowth pit structure, e.g., overgrowing dislocation 104, 106 and 108located at the base of the agglomerated pit structure 306. The lateralovergrowth continues (FIG. 3E) until islands coalesce to form asubstantially continuous film. In this example embodiment all thedislocations in initial III-nitride layer 100 have induced growth pitswhich have all intersected to produce a single agglomerated growth pitstructure. The ELO process is therefore capable of spanning the entireextent of the agglomerated growth pit preventing the propagation of theunderlying dislocations.

Finally, upon completion of the ELO process, the growth mode can bealtered to promote more vertical growth until the layer reaches adesired thickness (not shown). The resulting final layer thereby has areduced surface dislocation density in comparison to the initial layer.

The embodiment already briefly described with reference to FIG. 1B b(i.e., the deposition of a discontinuous layer of a dielectric maskingmaterial upon the intermediate layer or upon an etched (decorated)initial surface) is now described with further detail and elaborationwith reference to FIGS. 4A-E.

The methods of the embodiment commence utilizing the semiconductorstructure of FIG. 4A, which comprises a semiconductor structure similarto that of FIGS. 1B or 3C and formed by the same methods but alsoincluding a discontinuous masking layer. Therefore methods for theformation of the structures of FIGS. 1B or 3C are not repeated hereinfor brevity, but rather the additional steps involving formation of thediscontinuous masking layer and subsequent growth methods and structuresare described. Also, elements of FIGS. 4A-E that are closely similar tocorresponding elements of FIGS. 1A-D (and 1Bb) and 3A-E are identifiedwith the same reference numbers.

Turning now to FIG. 4A which comprises initial III-nitride layer 100(e.g. gallium nitride) formed on a suitable substrate 102 (e.g.sapphire). The initial layer 100 includes a plurality of dislocations104, 104′ and 108 which are utilized to produce agglomerated growth pitstructures 306 and growth pit structure 124 with crystalline facets 400in pitted intermediate layer 120 utilizing methods of the embodiments ofthe invention as previously outlined.

A thin layer of masking material 131 is applied to the surface of thepitted intermediate layer 120 producing the structure of FIG. 4B. Incertain embodiments of the methods of the invention the masking materialis deposited such that a discontinuous layer of a dielectric maskingmaterial is formed on the pitted intermediate layer 120 wherein portionsof the pitted intermediate layer (including crystalline facets 400 ofthe pits 306 and 124) are covered with masking material while otherportions of the pitted intermediate layer 120 are not so covered. Inaddition the discontinuous layer of the dielectric masking material 131may comprise a silicon nitride randomly distributed across the surfaceof the growth pits and the agglomeration of growth pits, as illustratedin FIG. 4B.

In greater detail, masking materials may comprise substances which actas anti-surfactants to III nitride growth, thereby limiting the amountof nucleation in masked portions of the structure of FIG. 4B. Depositionof anti-surfactant materials onto a secondary material may change thesurface growth kinetics by reducing the sticking coefficient (i.e. theprobability of adsorption of a chemical species on a surface). Thereforein the case of GaN the anti-surfactant may substantially preclude theadsorption and incorporation of Gallium onto the anti-surfactant surfaceand subsequently prevents the nucleation of GaN. In certain embodimentsthe anti-surfactant material may comprise dielectric materials; examplesof such materials may comprise silicon oxides, silicon nitrides andmixtures thereof.

As a non-limiting example, a silicon nitride may be utilized as adielectric masking material 131. The silicon nitride may be formeddiscontinuously on the surface of growth pit 124 and agglomerated growthpit structures 306 employing a number of methods known in the art, forexample. PVD, MBE, sputter deposition and spin-on coating techniques.However, it may be advantageous that the deposition of the dielectricmasking layer be performed in the reactor chamber utilized for theproceeding growth as it may be desirable to perform the entire growthprocedure within a single reactor so that a substrate being processed isnot exposed to atmosphere (as it would if ex-situ processing wereperformed). The ability to exclude ex-situ processing not onlysimplifies process protocols but also reduces operational costs due toequipment simplifications.

The discontinuous layer of dielectric masking material may be depositedby CVD processes, e.g., from gaseous silane (SiH₄) and ammonia (NH₃)under conditions known in the art. CVD reactors for producingIII-nitride materials frequently employ NH₃ as a Group V elementprecursor, therefore deposition of silicon nitride only requires theadditional of a SiH₄ input to the reactor chamber, along with anyadditional auxiliary fixturing. The growth thickness of the siliconnitride layer 131 is preferable maintained at a mean value betweenapproximately 5 Å and 30 Å, and preferably below approximatelypreferably 20 Å to further ensure the discontinuity of the masking layercoverage over pitted intermediate layer 120.

During the deposition of the thin, discontinuous layer of siliconnitride 131, a number of deposition parameters may be selected such thatthe dielectric masking material 131 is randomly distributed across theintermediate layer 120 such that the masking material 131 is randomlydeposited over single unagglomerated growth pits 124, agglomeratedgrowth pits 306 as well as the planar non-pitted material 126. Inaddition the discontinuous layer of dielectric masking material 131 maycover portions of the crystalline facets 400 of the pit structures 124,306 whilst leaving remaining portions of the crystalline facets 400 ofthe pits structures 124, 306 exposed and available for subsequent growthprocesses.

Silicon nitrides and silicon oxides (and other) masking materials aretherefore provided to substantially reduce nucleation and promotelateral growth from within some or all of the growth pits 124 and theagglomeration of growth pits 306 thereby allowing the enclosure of someor all of the growth pits and agglomeration of growth sides and furtherpromoting the reduction of dislocations in the following layer ofIII-nitride material.

In more detail, the semiconductor structure of FIG. 4C, illustrates theinitial stage of a plurality of lateral growth regions 402 from theexposed portions of growth pit structure 124 and agglomerated growth pitstructure 306. Lateral growth regions 402 may be seeded from the exposedportions of crystalline facets 400 of growth pit structures 124 andagglomerated growth pit structures 306. The initial stages of lateralgrowth regions 402 therefore nucleate from the exposed portions of thecrystalline facets 400 which are substantially free of dielectricmasking material. Growth parameters for enabling lateral growth areknown in the art and have been outlined previously. The lateral growthregions may comprise one or more free surfaces 406 which evolve (i.e.,proceed in the growth direction) with the continued grow of lateralgrowth regions 402. In certain embodiments the one or more free surfacesmay alter the propagation direct of a plurality of the emergentdislocations.

The semiconductor structure of FIG. 4D illustrates the epitaxial growthon the intermediate layer under third epitaxial growth conditionsselected to encourage lateral growth from within some or all of thegrowth pits and the agglomeration of growth pits. For example, continuedlateral growth of lateral growth regions 402 may be performed untillateral growth regions 402 coalescence to form coalesced lateral growthregions 402′. The lateral growth from exposed regions of the crystallinefacets of the growth pit structures and agglomeration of growth pitstructures may produce a plurality of functional cavities 404, whereineach of the plurality of functional cavities may comprise one or morefree surfaces 406 substantially free of dielectric masking material.

The one or more free surfaces 406 of the plurality of functionalcavities 404 may alter the propagation direction of a plurality of theemergent surface dislocation, such that a plurality of the emergentdislocations may intersect a plurality of the functional cavities. Forexample, emergent dislocations 104 of FIG. 4D are illustrated as bendingand intersecting function cavities 406 and emergent dislocation 108 isillustrated as intercepting functional cavity 402′.

Additional embodiments of the invention may also comprise terminating aplurality of the emergent surface dislocation (e.g., dislocations 104)on the one or more free surfaces 406′ of the functional cavities 404. Inmore detail, the one or more free surfaces of the functional cavitiesmay encourage the emergent surface dislocations to alter theirpropagation direction during the lateral growth process.

The free surface may act to prevent the further propagation of aplurality of the emergent surface dislocations such that the followinglayer of semiconductor material has fewer surface dislocations than theinitial semiconductor surface.

In other embodiments of the methods of the invention, an emergentsurface dislocation may alter propagation direction and intercept asecondary emergent surface dislocation. The two intercepting emergentsurface dislocation may annihilate each other when the emergent surfacedislocations have certain physical properties, i.e., when the twointercepting emergent surface dislocations have equal and oppositesBurgers vectors. Such an embodiment of the methods of the invention isillustrated in FIG. 4D by emergent dislocations 104′. As is evidentlyillustrated in FIG. 4D, emergent surface dislocations 104′ alterpropagation direction due to the methods of the invention (i.e.,including agglomerated growth pit formation, discontinuous maskingmaterial deposition and lateral growth) and intercept one anotherresulting in annihilation of dislocations 104′, and a further reductionin the dislocation density in the III-nitride material.

In other embodiments of the methods of the invention, the emergentsurface dislocations may not intercept and terminate on a free surfaceof a functional cavity and in addition may not intercept a secondaryemergent surface dislocation with equal and opposite Burgers vector. Insuch examples, the emergent surface dislocation may propagate throughthe semiconductor structure without being terminated. For example,emergent dislocation 108 of FIG. 4D is illustrated as interceptingfunctional cavity 404′. However, emergent dislocation 108 intercepts thedielectric masking material of functional cavity 404 and therefore maybereplicated in the following semiconductor material 132 (FIG. 4E) asemergent dislocation 108′.

The semiconductor structure of FIG. 4E illustrates the epitaxial growthof following semiconductor layer 132. Substantially continuous followingsemiconductor layer 132 may have fewer surface dislocations than theinitial semiconductor surface due the embodiments of methods of theinvention previously outlined.

As illustrated in FIG. 4E, emergent dislocations 104 may be terminatedon free surfaces 406′ of functional cavities 404 and therefore may notpropagate in following semiconductor layer 132. In addition, emergentdislocation 104′ may intercept and annihilate one another due to methodsof the invention and therefore such dislocations may not propagate intofollowing semiconductor layer 132. However, emergent dislocation 108 maypropagate past functional cavity 404′ and propagate into and throughfollowing semiconductor layer 132.

The embodiments of the invention may also comprise the semiconductorstructures formed by the outlined methods. For example, a groupIII-nitride semiconductor structure may comprise (see FIG. 4E) a firstlayer 408 comprising a plurality of functional cavities 404, whereineach functional cavity may comprise one or more free surfaces 406. Theone or more free surfaces 406 may be substantially free of a dielectricmasking material 131 whilst the plurality of functional cavities mayalso comprise one or more bound surface 410 adjoining the dielectricmasking material 131, bound surfaces 410 may comprise the surfaces ofthe functional cavities upon which masking material is deposited.

The semiconductor structure may also comprise a plurality ofdislocations 104, a plurality of the dislocations may intercept one ormore free surfaces 406′ of each of the function cavities 404 of thefirst layer 408, wherein a plurality of the dislocations may terminate.The semiconductor structure may also include a continuous followinglayer 132 overlying the first layer 408 having fewer dislocations thanin the first layer. In certain embodiments of the invention theplurality of functional cavities 404 may include an apex 412 withinfirst layer 408, the apex of the functional cavities may have a randomdistribution through out the thickness of the first layer, i.e., suchthat the apexes are positioned at differing thicknesses throughout thefirst layer.

An additional preferred embodiment repeats one or more times otherembodiments of the invention (e.g., the embodiment of FIGS. 1A-D, theembodiment of FIGS. 3A-E, or another embodiment), and is now describedwith reference to FIGS. 5A-D. Each following layer that results fromeach repeat can have successively improved quality.

Turning first to FIG. 5A, this figure illustrates a structure that canresult from performing once an embodiment of the invention. For brevityand convenience, this structure is illustrated as being the same as thestructure illustrated in FIG. 1D which has been produced by the stepsillustrated in FIGS. 1A-D. As illustrated in FIG. 5A (and FIG. 1D),dislocation 106 has propagated into and through semiconductor layer 132resulting in surface disturbance 130 on III-nitride surface 138. Inaddition dislocation 108, which was capable of producing a growth pitstructure but unable to intersect with other growth pit structures,propagates as dislocation 108 a upon coalescence over the growth pitstructure resulting in the emergence dislocation 134 at surface layer138.

Next, the previously described steps are applied to this structure. Themain bodies of FIG. 5B, FIG. 5C and FIG. 5D, illustrate the outcomeswhen steps similar and corresponding to the steps leading to FIG. 1B(and also FIG. 1B b), FIG. 1C and FIG. 1D respectively, are performedstarting with FIG. 5A. Alternatively, one or both of the dielectricmasking step illustrated in Fig. lBb and the etching step illustrated inFIG. 3B can also be performed during this repeat.

Turning first to the main bodies of FIGS. 5B-D, FIG. 5B illustratesgrowth of further pitted III-nitride layer 502 under the conditionspreviously outlined that promote formation of growth pits and theinterception of such growth pits to produce agglomerated pit structure500. Agglomerated growth pit structure 500 is induced by the surfacedisturbances at the surface emergence of dislocations 106 and 108 (whichpreviously had propagated through following layer 132 to surface 132).

FIG. 5C illustrates a further following layer 504, which as previouslydescribed, is initially grown over the agglomerated pitted regions ofpitted III-nitride layer 502 until coalescence of the separate growthfronts (FIG. 5D), thereby producing a final layer with reduceddislocation density. If necessary growth with a more vertical growthmode is then performed until further following layer 504 of a preferredthickness is formed.

As illustrated, dislocations 106 and 108 now induce growth pits whichintersect to form agglomeration area 500 in pitted layer 504, andsubsequent growth of another following layer 504 by ELO seals theagglomeration region. Accordingly, these additional dislocations areterminated at this layer and do not propagated into or through furtherfollowing layer 504. Thereby, the second following layer 504 will havebetter quality than the first following layer 132, which in turn willhave better quality than the initial layer 100. Specifically, thedensities of dislocations in layer 504 are less than in layer 132, whichin turn are less than in layer 100.

Finally, the invention includes semiconductor structures produced by themethods of this invention which have included within evidence that themethods of this invention have been performed one or more time. Such asemiconductor structure can include evidence of a single repetition ofthe embodiment, which as in FIG. 1D, typically comprises a plurality ofenhanced and intersecting dislocation structures, e.g., growth pits thatare intersecting one or more other growth pits and that are arrangedalong a plane internal to the structure. A further such semiconductorstructure can show evidence or two repetitions of the former embodiment.As in FIG. 5D, such evidence can typically include two or more spacedapart planes along which are arranged a plurality of intercepting growthpits forming a plurality of agglomerated pit structures. Preferably, thedensities of intercepting dislocation structures decrease from plane toplane towards the final surface.

The above described embodiments are intended to be exemplary but notlimiting. For example, methods of the invention can include differingnumbers of repetitions and differing arrangements of the basic steps ofthe invention, e.g., dislocation enhancement, dislocation intersection,and layer over growth, that are within the previously describedprinciples and goals of the invention. Further, in alternativeembodiments, dislocation enhancement can be performed by other thanpitted-layer growth or etching and so forth.

FIGS. 6A-B illustrates a gallium nitride structure produced by preferredembodiments of the invention. Specifically, a (0001) sapphire substratewas utilized for growth of an original GaN layer. (Note that a number ofprocess stages can be performed prior to growth including a substratecleaning cycle to remove unwanted contaminants (e.g. a high temperaturebake in hydrogen containing ambient), nitridization of the upper surfaceof the substrate, or further surface pretreatments dependent on thechemistry of both the growth material and the base substrate.) GalliumNitride layer 100 growth commenced with deposition of a nucleation layerat a temperature of approximately 500° C. for a period of 20 mins. Thetemperature of the reactor was subsequently raised for thermal treatmentof the nucleation layer and the growth of high quality gallium nitride.In this example the temperature in the reactor was raised to atemperature of 1100° C. in a time period of 20 mins and growth wascarried out for 90 minutes to produce a layer thickness of approximately1.0-2.5 μm. The temperature of the reactor was then reduced toapproximately 890 ° C. for the growth of the pitted intermediate layer120, in this example the reduced temperature growth was continued for 90mins until a pitted layer thickness of approximately 150 nm is produced.

FIG. 6A provides an image produced via an atomic force microscope (AFM)of the GaN structure after completion of the above steps (schematicallyillustrated in FIGS. 1A and 1B). As noted the surface comprised highquality gallium nitride 600 and dark hexagonal surface openings of pitlike structures, example pit like structures 602 and 604. Pit structuressimilar to pit structure 604, are single unclustered growth pits and areanalogous to the growth pit produced via dislocation 108 in FIG. 1B. Pitstructures similar to pit structure 602 are agglomeration areas wheretwo or more growth pits have intersected and are analogous to structure122 in FIG. 1B. (Only selected clustered structures have been labeled;other clustered structures are apparent in this figure.) Agglomeratedpit structures similar to pit structure 602 have increased lateralextent of their surface openings in the III-nitride layer in comparisonto individual pit structures similar to pit structure 604.

The example gallium nitride surface 600 shown in FIG. 6A was well suitedfor further growth processes, e.g. lateral overgrowth of the growth pitsand pit agglomeration areas for producing a following low-dislocationgallium nitride material. The structure was replaced in the growthreactor and the temperature and precursor flow parameters for theinitial stages of bulk growth were optimized for ELO, resulting in a 2Dgrowth mode. Upon III nitride coalescence into a continuous film theflow parameters were again varied for growth of the remaining bulk GaNmaterial

FIG. 6B shows a cross section transmission electron micrograph (TEM)image of the III-nitride sample upon completion of the lateralovergrowth stage of the process (schematically illustrated in FIGS. 1Cand 1D). The lower portion (below the horizontal dotted line) of thisTEM image corresponds to the intermediate pitted layer 118 of FIG. 1Dand is labeled as such. The upper portion is analogous to the followinglayer of III-nitride material produced by lateral overgrowth, i.e.region 132 of FIG. 1D and is again labeled as such.

The region within circle 606 illustrates a single growth pit produced bydislocation 608. Upon lateral overgrowth and coalescence, the originaldislocation propagated as dislocation 608 a within the following layerof III-nitride material. This illustrates that a single unclusteredgrowth pit may not be successful in preventing dislocation propagation.

The region within circle 610 illustrates an agglomerated area formed byintersection of the plurality of growth pits induced by dislocations612. The outline of a number of intersecting growth pit structures canbe discerned within region 610; specifically, growth pit 614 intersectsother growth pits. In the upper portion above the dotted line, it can beseen that GaN has laterally overgrown agglomeration 614 and that none ofthe original dislocations 512 are visible. It is believed thatdislocations 612 have been terminated by the agglomeration andovergrowth processes of the invention. Therefore, the number ofdislocations in the lateral overgrowth region 132 is less than thenumber of dislocation in the lower region 118. A final surfacedislocation density of gallium nitride on the order of less than 5×10⁷cm⁻² was observed.

It should be understood that for the examples give above the describedphysical parameters, e.g. times, temperatures etc are exemplary only andare not to be taken as limiting. For example, the growth temperaturerange, growth time, etc are suitable for III-nitride, e.g., GaN. Forother III-nitride materials these parameters can be different.

EXAMPLES

The following examples and reports of experiments illustrate etchpitting, enlargement of pits, amorphous Si₃N₄ deposition and epitaxiallateral overgrowth (ELOG) that were carried out on a two-step GaNsubstrate to develop the optimum protocols for the reduction ofthreading dislocations.

In the GaN etch pit studies, ex-situ aqueous KOH etching, molten KOHetching, and in-situ SiH₄ etching were carried out at temperatures of80° C., 260° C., and 860° C. with different etching periods in the rangeof 0 to 10 mins, respectively. Ex-situ aqueous KOH etching (Han et al.Scripta Materialia 59 1171 2008) and an in-situ SiH₄ etching method wereused to delineate etch pits associated with dislocations and todetermine threading dislocation density. In general, a transmissionelectron microscope (TEM)-based technique could be used to reveal alltypes of threading dislocations (TDs) and to measure the TD density inGaN with high contrast over a relatively large area. As this requirestime-consuming sample preparation and significant skill, a simple,fast-turnaround technique has been developed to provide quick feedbackduring an ongoing series of growth experiments.

One method for etching pits is conducted using low-temperature KOH wetetching and atomic force microscopy (AFM) was carried out on MOCVD andHVPE GaN samples to determine TD density. There was no termination ofatomic steps and structure. An improved method for detecting threadingdislocations (TDs) in GaN epitaxial layers grown on (0001) sapphireincluded the use of aqueous KOH etching maintained at 80° C. for 10 min.The etching rate for this solution was higher surrounding thedislocation region compared to dislocation-free areas due to the strainassociated with them and pits are formed at TDs after etching. Withthese ex-situ KOH etchings, however, more cleaning steps were needed toremove residues that remain from the etching process.

An in-situ surface treatment in which GaN is exposed to a SiH₄ flux at860° C. in the presence of NH₃ for 240 sec exposure was developed todetermine TD density. Pits associated with screw or mixed-type TDs werefound to have more than doubled in diameter, as measured by AFM. Thesepits are associated with step-edge terminations. Additional small pitshad appeared, not associated with step-edge terminations, which arebelieved to relate to edge-type TDs. This in-situ treatment was used todevelop a growth protocol due to simple process in MOCVD.

Studies using the in-situ SiH₄ etching and low temperature GaN growthfor increasing etch pit sizes and clustering etch pits were alsoperformed at different growth temperatures, various etching durationsand VIII ratio. The enlargement or clustering of pits help with theplacement of amorphous material in enlarged pits. An in-situ Si₃N₄deposition in pits for blocking and bending dislocations was studied atdifferent deposition durations, temperatures and annealing time. The keygrowth details of ELOG GaN samples were investigated where reduction ofthreading dislocations density has been attempted and what reductionmechanism has been shown.

Pits were produced on dislocations by different techniques:

Aqueous KOH Etching

The KOH etching experiments were carried out using a 45% KOH: H₂O (1:3)aqueous solution maintained at 80° C. as a function of time. The GaNsamples used for KOH etching were grown by MOCVD and HVPE. Awell-defined step-terrace structure was obtained where three kinds ofetch-pit related to three different types of TDs are clearly observed onthe etched surface. TDs identified as screw type TDs appear on steps orat the end of steps, mixed type TDs appear at the end of steps and edgetype TDs appear on the terraces. The threading dislocation density is 3to 4×10⁸/cm². AFM characterization results of surface topologiesassociated with etch-pits after KOH etching exhibited three differenttypes of TDs. An asymmetry in depth profile across edge-type TDs wasobserved. The topological profile from screw TDs is symmetric, and forthe mixed type the profile was found to be asymmetric. All types ofdislocations are clearly observed on the surface due to pit formation,but the pit size and depth were found to be different for the threedifferent TDs due to the differing strains associated with each one.Etch pits after aqueous KOH are hexagonal for screw type dislocationsand polygonal for mixed and edge type dislocations, with sizes rangingfrom 40 to 110 nm in diameter and from 0.4 to 12 nm in depth.

Molten KOH Etching

To produce larger pits as a function of time, molten KOH etching at 280°C. was utilized. The etch pits observed after molten KOH etching are ofhexagonal and polygonal shapes revealed by AFM and their size range from100 to 600 nm in diameter and 50 to 200 nm in depth. Molten KOH etchingwas very aggressive, however, such that it can be difficult to ascertainthe location of the pits due to the disappearance of atomic stepsbecause of the high etching rate on the GaN surface.

In-situ SiH4 Etching.

As noted, these ex-situ etching methods require cleaning after chemicaletching. To prevent contamination and reduce the time, in-situ SiH₄etching was carried out in a MOCVD reactor as a function of temperatureand time. Two-step GaN samples were etched with SiH₄ flux of 5 mL/minand NH₃ flux of 2 L/min for 3 to 5 mins at temperatures between 860° C.to produce pits. After etching, many etch pits appeared on the GaNsurface. Again, three types of etch pits related to three differenttypes of TDs on the etched surface were encountered a temperature of860° C. As the etching temperature was increased, the pit sizes becomelarger but 860° C. was found to be optimum for pit growth for theseexamples.

Longer in-situ SiH₄ etching and low temperature GaN growth can be usedto increase pit sizes, leading to their agglomeration. If pits areagglomerated with depth ranges of 200-450 nm, it is then easier todeposit in-situ amorphous silicon nitride therein. Surface featuresobserved on the GaN surface as a function of SiH₄ etching at 860° C. for10 mins on a GaN substrate (TDD=2×10⁹/cm²) helps agglomerate pits but itresults in a rough surface and wide pits. The etched low TDD GaN for 10mins has more agglomerated pits than the etched GaN for 5 mins. Some ofagglomerated pits are still too big which needs more coalescence time.Based on this, 5 mins etching duration was found to be much moresuitable for both standard and low TDD GaN layers. Results show TDDsafter etching at 850° C. and 860° C. are about 3.5×10⁸/cm² and about3×10⁸/cm², respectively and it is quite similar to TDD (about3.2×10⁸/cm²) of aqueous KOH etched GaN mentioned above. However, TDDsafter etching at 870° C. and 880° C. are about 2.7×10⁸/cm² and1×10⁸/cm², respectively. This indicates the GaN surfaces may beover-etched and decomposed at those etching temperatures under highergas flow.

Thus, etching temperatures between 850° C. and 860° C. at about 5minutes are advantageous conditions to increase pit size and to openessentially all pits in the GaN epilayers. As growth temperaturesincrease, the agglomerated pit shape changes from hexagons to ovals orcircles. The density of pits reduces as increasing growth temperaturescause secondary growth. This is believed to be why low temperature GaNgrowth at 860° C. helps agglomerate and open all pits. The TDD aftergrowth at 860° C. is about 3×10⁸/cm², while TDDs after secondary growthat 870° C. and 880° C. are about 1.1×10⁸/cm² and 7×10⁷/cm²,respectively. The smaller pits are covered by lateral overgrowth atthose deposition temperatures. The SiH₄ etching produced pit sizesranging from 50 to 150 nm in diameter and from 2.5 to 30 nm in depthwhich were hexagonal for screw type dislocations and polygonal for mixedand edge type dislocations.

Additional Etchants

There are additional etching methods for defect delineation. HClvapor-phase etching of GaN at 600° C. can lead to the formation of threedistinct etch pits related to edge (polygon shape), screw (well-definedhexagon shape) and mixed types (unclear hexagons) of dislocations, withall pits wider than 600 nm. Various hot etching solutions, such asH₃PO₄, can etch GaN anisotropically and form pits on the surface byusing PEC etching. The resulting etch-pits are hexagonal and polygonal,with sizes ranging from 100 to 600 nm in diameter and from 50 to 200 nmin depth.

Etching Enhancers

As the formation and enlargement of etch-pits on dislocations withvarious etchings on GaN is inert due to its wide band gap and highbonding enthalpy, an additional driving force, such as lasers orultraviolet light, can be used to assist in the etching. Laser or UVenergy can be applied to the substrate along with the application of theetchant.

In general, the etching rate is higher surrounding the dislocationregion compared to the dislocation free areas due to the strainassociated with them. As a result, pits are formed at TDs after etching.A method of characterizing TDs in GaN is defect-selective etching, whichreveals not only the dislocation density but also, by selective etching,the dislocation character. The specific etch pit formation is dependenton the etchant and processing conditions used but a skilled artisan candetermine the optimum conditions for any particular II-V substrate.

Etch pits associated with screw or mixed type TD were found to have morethan doubled in diameter after etching, as measured by AFM. These pitsare associated with step-edge terminations or step bunch. The elasticenergy of the dislocation will be relaxed at the free surface and willgive rise to a step there. The formation of a growth step at the freesurface is dependent on the presence of a dislocation whose Burgersvector is inclined with respect to the free surface. Screw type TDsappear on steps or at the end of steps, mixed type TDs appear at the endof steps. Additional small pits had appeared, not associated withstep-edge terminations, which are believed to relate to edge type TDs onthe terraces.

The observations show that molten KOH pit sizes are larger than thoseGaN samples etched with aqueous KOH and in-situ SiH₄. High temperaturewas used to accelerate etching for easy detection of pits associatedwith various types of TDs. It is possible that the formation of largerpits may obscure many small pits related to edge TDs and the highetching rate results in the disappearance of atomic steps on the GaNsurface. This may prevent establishing any relation between TDs andatomic step-terrace structure, which is important for the identificationof different TDs. So, it is not possible to distinguish between thethree kinds of etch pits related to the three different TDs.

The above ex-situ etching methods required more extensive cleaning afterchemical etching. Therefore, in-situ SiH₄ etching was preferred overex-situ etching. In addition, it required less time and also reduces thecost to produce the desired defect selective etching by removing therequirement for loading and unloading of the materials between growthand etching stages.

As GaN decomposes at a temperature of 860° C. at a pressure of 100 Ton-of pure hydrogen, it is advantageous to conduct etching at processconditions that are below those values. With SiH₄ etching attemperatures of 960° C. to 1060° C., surface roughening occursapparently due to the GaN decomposition. At lower temperatures, e.g., at860° C. or below, in-situ SiH₄ etching provided well definedstep-terraces and etch pits without surface damage of the etched GaN.The etching increases the pit size and enlarges pits associated withTDs. Pits on mixed type dislocations ranged in size from approximately85 nm in width and 6 nm in depth, while pit size on edge typedislocation is approximately 50 nm in width and 3 nm in depth. AFMevaluation of the etched GaN surfaces reveals that most dislocations inthe GaN buffer layer are edge and mixed type, while screw dislocationsare rarely observed. Edge type and mixed type dislocations eachcontribute approximately half of the total dislocations density in thisarea of the GaN layer.

Additionally, for GaN surfaces exposed to SiH₄ for very long times, 10min or more, we growth of amorphous SiN_(x) can occur. To avoid anydeposition during etching, shorter times, e.g., 5 min, of etchingduration are preferred.

The preferred embodiments of the invention described above do not limitthe scope of the invention, since these embodiments are illustrations ofseveral preferred aspects of the invention. Any equivalent embodimentsare intended to be within the scope of this invention. Indeed, variousmodifications of the invention in addition to those shown and describedherein, such as alternate useful combinations of the elements described,will become apparent to those skilled in the art from the subsequentdescription. Such modifications are also intended to fall within thescope of the appended claims. In the following (and in the applicationas a whole), headings and legends are used for clarity and convenienceonly.

A number of references are cited herein, the entire disclosures of whichare incorporated herein, in their entirety, by reference for allpurposes. Further, none of the cited references, regardless of howcharacterized above, is admitted as prior to the invention of thesubject matter claimed herein.

1. A Group III-nitride semiconductor structure comprising a first layerhaving a surface and agglomerations of growth pits located beneath thesurface in the structure in place of propagating defects, wherein thegrowth pits present voided regions that gradually increase in sizetowards the surface of the first layer, and have one or more sides thatare at least partially covered with masking material to prevent growthof semiconductor material on the partially covered side(s).
 2. Thestructure of claim 1, wherein the masking material forms a discontinuouslayer upon the first layer and has a thickness of less thanapproximately 20 Å.
 3. The structure of claim 1, wherein the maskingmaterial is a dielectric material of a nitride or oxide.
 4. Thestructure of claim 1, wherein the voided regions are shaped, sized, andarranged so as to have polygonal, circular or oval openings withgenerally conical or cylindrical shapes that extend down along theprincipal axis of the dislocation, generally gradually narrowing withdepth from their widest portions located closer to or at the surface ofthe first layer.
 5. The structure of claim 1, wherein a plurality of thevoided regions have a narrower apex within the first layer at which atleast one defect terminates, and have broader bases toward the surfaceof the first layer.
 6. The structure of claim 5, wherein growth pitshave an inverted-pyramid-type form and include a dislocation located atthe apex of the inverted pyramid type structure.
 7. The structure ofclaim 1, wherein the agglomerations of growth pits have lateral extentsof less than about 5 μm.
 8. The structure of claim 1, wherein thethickness of the first layer is less than about 1 μm.
 9. The structureof claim 1, further comprising a substantially continuous lateralovergrowth layer upon the first layer and masking material and aplurality of functional cavities in the first layer.
 10. The structureof claim 9, wherein the functional cavities include one or more freesurfaces that are substantially free of masking material and one or morebound surfaces adjoining the masking material.
 11. The structure ofclaim 10, further comprising dislocations that intercept one or more ofthe free surfaces of the functional cavities of the first layer, whereinthe dislocations terminate.
 12. The structure of claim 11, wherein thefunctional cavities include apexes and are randomly distributedthroughout the first layer such that the apexes are positioned atdiffering depths throughout the first layer.
 13. A method for forming aIII-nitride semiconductor structure upon an initial III-nitride surfacehaving a plurality of emergent dislocations, which method comprises:opening growth pits associated with the emergent dislocations in theinitial III-nitride surface; intersecting two or more of the growth pitsinto agglomerations of growth pits; and lateral growing of a followingIII-nitride layer on pit surfaces at least until the following layer hassubstantially continuous lateral extent, and wherein the lateral growthnucleates from portions of growth pits to form a plurality of enclosedfunctional cavities which are intercepted by emergent dislocations toform the following layer with a dislocation density that is less thanthat of the initial surface.
 14. The method of claim 13, wherein thelateral growing is conducted at a temperature of less than 950° C., apressure of greater than about 100 mb, or both.
 15. The method of claim13, which further comprises repeating one or more times the opening,intersecting and lateral growing within a single reactor chamber withoutx-situ processing.
 16. The method of claim 13, wherein the opening andintersection of growth pits continues as long as a plurality ofindividual growth pits have lateral extents of less than about 5 μm.17-19. (canceled)